JP2007230024A - Facing film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inexpensive facing film excellent in three-dimensional curved surface followability, weatherability, scratch resistance and chemical resistance. <P>SOLUTION: The facing film has a base material layer 2 formed from a polyolefinic resin and a topcoating layer 1 and is characterized in that the topcoating layer 1 is formed using a polycarbonate urethane resin, hexamethylene diisocyanate and isophorone diisocyanate and the mixing ratio of hexamethylene diisocyanate and isophorone diisocyanate is 9:1-6:4 and a mass ratio. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to an exterior film.

The exterior film is a film that is affixed for the purpose of protecting the design and the surface, for example, for advertising purposes and for vehicles, in place of conventional painting, and is made of synthetic resin or the like. As this film, there is also used a film coated with an adhesive so that it can be easily attached to a base material made of a metal such as iron or aluminum, or a resin such as acrylic or carbonate. Yes.

Conventionally, a film made of polyvinyl chloride resin (PVC) has been used as such an exterior film, but from the viewpoint of environmental protection, an alternative to a non-chlorinated material has been demanded. And those using polyolefin resins such as acrylic resin, polyethylene, polypropylene, and TPO. However, for example, the acrylic resin itself is very hard and has a problem that it is easily broken when processed into a film and has little elongation.

Polyolefin resins, on the other hand, are more flexible than acrylic resins, but have insufficient scratch resistance and chemical resistance, and lack of vividness in color tone, which tends to be whitish. It was.
Patent Document 1 discloses an automobile exterior having excellent weather resistance, scratch resistance, and decorative effect by having a base material of an olefin resin having an adhesive function and a top coat layer of a urethane resin supported by the base material. A film is disclosed. However, this urethane resin is disclosed only from acrylic polyol and polyisocyanate, and polycarbonate urethane resin is not studied. In addition, chemical resistance has not been sufficiently studied.

Therefore, it is non-PVC and has flexibility like PVC, it is not whitened during bending or stretching in post-processing, and has excellent followability to a three-dimensional curved surface, as well as weather resistance, scratch resistance, chemical resistance There has been a need for an exterior film having excellent properties.

JP 2003-225977 A

In view of the above situation, an object of the present invention is to provide an inexpensive exterior film excellent in three-dimensional curved surface followability, weather resistance, scratch resistance, and chemical resistance.

The present invention is an exterior film having a base material layer formed using a polyolefin-based resin and a topcoat layer, and the topcoat layer uses a polycarbonate-based urethane resin, hexamethylene diisocyanate and isophorone diisocyanate. The exterior film is characterized in that the mixing ratio of the hexamethylene diisocyanate and the isophorone diisocyanate is 9: 1 to 6: 4 by mass ratio.

The topcoat layer is preferably formed using a zinc-based compound as a catalyst.
The thickness of the top coat layer is preferably 2 to 50 μm.
The exterior film of the present invention preferably further has a pressure-sensitive adhesive layer.
The exterior film of the present invention preferably further has a release layer.
Hereinafter, the present invention will be described in detail.

The exterior film of the present invention has a base material layer formed using a polyolefin-based resin and a topcoat layer, and the topcoat layer includes a polycarbonate-based urethane resin, hexamethylene diisocyanate, and isophorone diisocyanate. The mixing ratio of the hexamethylene diisocyanate and the isophorone diisocyanate is 9: 1 to 6: 4 in terms of mass ratio. For this reason, it is excellent in scratch resistance, chemical resistance, weather resistance and curved surface followability.

The exterior film of the present invention has a base material layer formed using a polyolefin-based resin and a topcoat layer formed using a polycarbonate-based urethane resin. Only the base material layer has insufficient scratch resistance and chemical resistance, and these properties can be greatly improved by forming a topcoat layer. Further, it has good flexibility, has flexibility and strength like soft vinyl chloride, and has excellent curved surface followability particularly during bending. Furthermore, even when processed into a film shape, the color tone is excellent without whitening.

The urethane resin has various compositions, and examples thereof include polyester, polycarbonate, polyether, lactone, and acrylic. In conventional films, polyester is most commonly used as a urethane resin, but it is weak against chemicals containing alcohol such as isopropyl alcohol, and the cloudiness phenomenon becomes noticeable when it comes into contact. Since the exterior film of the present invention has a topcoat layer made of a polycarbonate urethane resin, it has good scratch resistance and chemical resistance. Further, flexibility for pasting can be satisfied at the same time.

The exterior film of the present invention also has good weather resistance and chemical resistance because the top coat layer is formed by mixing two specific polyisocyanates at a specific ratio. Hexamethylene diisocyanate alone has poor acid durability and develops a cloudiness phenomenon upon contact. On the other hand, isophorone diisocyanate has a characteristic that it is inferior in durability to alcohols although it has good durability to acids. In the present invention, by mixing them at a specific ratio, the above-mentioned scratch resistance, curved surface followability, weather resistance, and chemical resistance against various chemicals are both achieved. In this specification, “film” refers to a concept including “sheet”.

Examples of the polycarbonate-based urethane resin include those obtained by reacting a carbonate polyol, a polyisocyanate compound and, if necessary, a chain extender by a conventionally known production method. Polycarbonate polyol is synthesized by, for example, phosgenation of polyol, transesterification with diphenyl carbonate, condensation polymerization of dibasic acid and glycols, or the like. Examples include products obtained by reacting 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol or tetraethylene glycol with a diaryl carbonate such as diphenyl carbonate or with phosgene. It is done. With respect to the condensation polymerization method of dibasic acid and glycols, for example, a method in which a dihydric phenol as a dibasic acid and a cyclic diol such as glycol carbonate as a glycol are subjected to condensation polymerization. Moreover, the polyester polycarbonate obtained by reaction with polycarbonate diol, dicarboxylic acid, or polyester may be sufficient.

Examples of the polyisocyanate compound include 1,6-hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexamethylene diisocyanate, lysine methyl ester diisocyanate, methylene diisocyanate, isopropylene diisocyanate, lysine diisocyanate, 1,5- Aliphatic polyisocyanate compounds such as octylene diisocyanate and dimer acid diisocyanate; 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate (IPDI), hydrogenated tolylene diisocyanate, 2,4 or 2,6-methylcyclohexane diisocyanate, isopropylidene Fats such as dicyclohexyl-4,4'-diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate) 2,4 or 2,6-tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate, xylylene diisocyanate (XDI), tetramethylxylylene diene Mention may be made of aromatic polyisocyanate compounds such as isocyanate, cyclohexanephenylene diisocyanate, triphenylmethane triisocyanate, tris (4-phenylisocyanate) thiophosphate, tolidine diisocyanate, p-phenylene diisocyanate, diphenyl ether diisocyanate, diphenylsulfone diisocyanate. These may be used alone or in combination of two or more. Among these, when considering outdoor use, an aliphatic polyisocyanate compound and an alicyclic polyisocyanate compound which are non-yellowing types represented by HDI that do not cause discoloration (yellowing) are preferable.

As the chain extender, a compound containing at least two functional groups containing an active hydrogen atom reactive with an isocyanate group can be used. For example, water, ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, 1,5-hexanediol, ethylenediamine, 1,2-propylenediamide, triethylenediamine, decamethylenediamine, isophoronediamine, m-xylylenediamine , Dimethylhydrazine, dicarboxylic acid, hydrogen sulfide and the like. Amine-based materials are not preferred because they do not produce urea-soluble urea bonds.

Examples of commercially available polycarbonate urethane resins include U5635G-3 (trade name, manufactured by Seiko Kasei Co., Ltd.), U5635G-6 (trade name, manufactured by Seiko Kasei Co., Ltd.), and the like.

In the exterior film of the present invention, when the top coat layer is formed, hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI) are blended in addition to the polycarbonate urethane resin. By using the above two types of non-yellowing isocyanate, a film excellent not only in scratch resistance and weather resistance but also in chemical resistance such as alcohol resistance and acid resistance can be obtained.

The mixing ratio of HDI and IPDI (HDI: IPDI) is 9: 1 to 6: 4 by mass ratio. When the mixing ratio of the HDI exceeds 90%, a problem occurs in acid resistance, and the clouding phenomenon becomes remarkable. If the mixing ratio of the HDI is less than 60%, a problem occurs in the alcohol resistance, and the chemical contact trace becomes conspicuous. The mixing ratio is preferably 8: 2 to 6.5: 3.5.

It is preferable that the compounding quantity of the said isocyanate component (total amount of HDI and IPDI) is 5-15 mass parts with respect to 100 mass parts of said polycarbonate-type urethane resin solid content. If it is less than 5 parts by mass, the chemical resistance, scratch resistance and weather resistance may be lowered due to insufficient curing. When it exceeds 15 parts by mass, there is a risk of appearance abnormality such as whitening due to residual isocyanate. As for the said compounding quantity, it is more preferable that it is 5-10 mass parts.

In the exterior film of the present invention, it is preferable to use a zinc-based compound as a catalyst when the top coat layer is formed. In consideration of durability against acids, alcohols, etc., tin-based catalysts are preferable, but it is preferable not to use heavy metals as environmental considerations. Examples of such a tin substitute material include catalysts such as amine, bismuth, zirconium, and zinc, but it is preferable to use a zinc-based compound because it has the highest alcohol resistance.
Examples of the zinc compound include zinc oxide and zinc 2-ethylhexanoate.

As a compounding quantity of the said zinc type compound, it is preferable that it is 0.1-2.0 mass parts with respect to 100 mass parts of polycarbonate-type urethane resin solid content. If it is less than 0.1 parts by mass, the alcohol resistance may not be improved. If it exceeds 2.0 parts by mass, the pot life of the coating solution may be shortened, making it difficult to process. The blending amount is more preferably 0.2 to 1.5 parts by mass.

In addition to the composition for adjusting the gloss, the top coat layer may contain various functional agents such as an ultraviolet absorber, a light stabilizer, an antistatic agent, and a colorant so as not to interfere with the effects of the present invention. You may add in the range.

The thickness of the top coat layer is preferably 2 to 50 μm. If it is less than 2 μm, the intended function may not be obtained. If it exceeds 50 μm, the film and the sheet become hard, the curved surface followability is deteriorated, and there is a possibility that whitening phenomenon occurs at the time of bending processing or floating after sticking occurs. The thickness is more preferably 5 to 40 μm.

The exterior film of the present invention has a base material layer formed using a polyolefin resin.
The polyolefin resin is not particularly limited, and a conventionally known polyolefin resin used for an exterior film can be used. From the group consisting of a polypropylene resin, a polyethylene resin, and an olefin thermoplastic elastomer. It is preferable that it contains at least one selected.

The polypropylene resin is not particularly limited, and examples thereof include homopolymerized polypropylene (h-PP), random copolymerized polypropylene (r-PP), and block copolymerized polypropylene (b-PP). Among them, the homopolymerized polypropylene has a melting point that is too high and may be insufficiently melted by calendering, and the film using the block copolymerized polypropylene may be whitened when bent. Therefore, the random copolymerized polypropylene is preferable. . The polypropylene resin may be a copolymer obtained by a monomer composition containing other monomers within a range not impairing the effects of the present invention.

Examples of commercially available polypropylene resins include WT2002A (polypropylene resin, manufactured by Nippon Polypropylene), Chisso Polypropylene F8577, F3020, F8090, XF9520 (polypropylene resin, manufactured by Chisso), J-Alomer PB222A (polypropylene resin, Nippon Polyolefin). For example).

The polyethylene resin is not particularly limited, and examples thereof include high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and very low density polyethylene (VLDPE). . Among these, low density polyethylene is preferable from the viewpoint of obtaining a film excellent in followability to a curved surface. The polyethylene-based resin may be a copolymer obtained by a monomer composition containing other monomers within a range that does not impair the effects of the present invention.

Examples of the commercially available polyethylene resin include KF-280 (low density polyethylene resin, manufactured by Nippon Polypropylene), Hi-Zex 8200B, 6300M (manufactured by Mitsui Chemicals), Kernel KS-340, KS-560, and KS-570. (Nippon Polychem Co., Ltd.).

The olefin-based thermoplastic elastomer (hereinafter also referred to as TPO) is not particularly limited, and conventionally known olefin-based thermoplastic elastomers can be used. An ethylene-propylene copolymer component and / or a polybutylene component and a polypropylene component are used. It is preferable that it is a copolymer. Such a copolymer is composed of a crystalline polypropylene resin as a hard segment and an ethylene-propylene rubber component or a butyl rubber component as a soft segment. By adjusting the ratio of the hard segment and the soft segment, Various physical properties can be obtained. The olefinic thermoplastic elastomer may be a copolymer obtained by a monomer composition containing other monomers within a range that does not impair the effects of the present invention.

As a method for producing the olefinic thermoplastic elastomer, a conventional method is used in which a hardener and a soft segment are mixed with a crosslinking agent or plasticizing oil as necessary, melt kneaded using an extruder, and crosslinked. In recent years, a method for directly producing the hard segment and the soft segment by a polymerization reaction is also known, in particular, an olefinic thermoplastic elastomer produced by the latter method is produced in a reactor. It is called reactor TPO because it is an olefinic thermoplastic elastomer.

A commercially available product can be suitably used as the reactor TPO. As a specific example of such a commercial product of the reactor TPO, for example, P.O. E. R R210E, P.I. E. RT310J, P.I. E. R R110E (all have a melt flow rate of 1.5 g / 10 min), Catalloy KS-353P (melt flow rate 0.45 g / 10 min) manufactured by Montell-JPO, R-110E manufactured by Idemitsu Co., etc. be able to.
These may be used alone or in combination of two or more.

In particular, the base material layer is preferably obtained from a mixture of polypropylene, low-density polyethylene, and olefinic thermoplastic elastomer in terms of texture (rigidity), surface smoothness, and resistance to whitening during stretching.
In the polyolefin-based resin, the mixing ratio of polypropylene, the low-density polyethylene resin, and the olefin-based thermoplastic elastomer is preferably 40 to 90/20 to 50/40 to 10 in terms of mass ratio. If it is out of the above range, the above-mentioned characteristics may be impaired.

For the base material layer, if necessary, a lubricant, an antioxidant, a heat stabilizer, an ultraviolet absorber, a light stabilizer, a pigment, a modifier, a flame retardant, an antistatic agent, a reinforcing agent, a tackifier, An appropriate amount of known additives generally added to the resin, such as fillers and fungicides, may be added.

Examples of the lubricant include fatty acids such as stearic acid; fatty acid metal soaps having 12 to 30 carbon atoms such as calcium stearate, magnesium stearate, barium stearate, calcium laurate, and barium laurate; stearamide, oleamide, Examples include acid amides such as esylamide, erucamide, and various waxes. These may be used alone or in combination of two or more.

Examples of the antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,6-dicyclohexyl-4-ethylphenol, octadecyl-3- (3,5-di-t-butyl- Phenolic antioxidants such as 4-hydroxyphenyl) propionate, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate]; trioctyl phosphite, tristridecylphos And organic phosphite antioxidants such as phyto; sulfur antioxidants such as dilauryl thiodipropionate and pentaerythritol tetralauryl thiopropionate. These may be used alone or in combination of two or more.

Although the thickness of the base material layer can be used in various thicknesses depending on the purpose of use of the film, etc., the thickness is usually preferably in the range of 0.04 to 0.3 mm. 0.04. If it is less than mm, it may not be possible to have a sufficient support function. If it exceeds 0.3 mm, the appearance and the curved surface followability may be deteriorated.
The thickness of the base material layer is more preferably 0.05 to 0.25 mm.

In the exterior film of the present invention, the substrate layer and the topcoat layer can be used in various layer configurations. Preferably, the substrate and the topcoat layer can be used in a two-layer structure.

The exterior film of the present invention may further have an adhesive layer. For example, the film which laminated | stacked the topcoat layer, the base material layer, and the adhesive layer in this order is mentioned.
The said adhesive layer can be formed with a conventionally well-known coating method using an adhesive. The pressure-sensitive adhesive is not particularly limited, but an acrylic pressure-sensitive adhesive is preferable from the viewpoints of adhesion to an adherend and adhesive strength.
The acrylic pressure-sensitive adhesive is a pressure-sensitive adhesive containing an acrylic polymer, specifically, a copolymer composed of 2-ethylhexyl acrylate and acrylic acid, and a copolymer composed of 2-ethylhexyl acrylate and hydroxyethyl acrylate. A copolymer consisting of 2-ethylhexyl acrylate and methyl methacrylate, a copolymer consisting of 2-ethylhexyl acrylate, 2-methoxyethyl acrylate and vinyl acetate, a copolymer consisting of 2-ethylhexyl acrylate and vinyl pyrrolidone, Examples thereof include a copolymer composed of 2-ethylhexyl acrylate, methyl methacrylate and 2-methoxyethyl acrylate, a copolymer composed of 2-ethylhexyl acrylate, vinyl pyrrolidone and acrylic acid. These may be used alone or in combination of two or more.
Examples of commercially available adhesives include SK Dyne 1340 (acrylic, manufactured by Soken Chemical Co., Ltd.).

The pressure-sensitive adhesive layer preferably has a thickness of usually 3 to 50 μm. If the thickness is less than 3 μm, sufficient adhesion and adhesive strength may not be obtained. Even if it exceeds 50 μm, an improvement in the effect cannot be expected, which may be disadvantageous economically. The thickness is more preferably 5 to 30 μm.

The exterior film of the present invention may further have a release layer in addition to the top coat layer, the base material layer, and the pressure-sensitive adhesive layer. The release layer is a sheet that is peeled off when attached to an adherend. The said release layer is laminated | stacked on the surface on the opposite side to the side by which the base material layer is affixed in an adhesive layer.

As the mold release layer, for example, a film having a mold release treatment applied to the surface to be attached to the pressure-sensitive adhesive layer can be used.
The material of the film subjected to the release treatment is preferably an olefin resin film. Thereby, the mold release layer excellent in smoothness can be formed, and the adhesive layer surface after peeling of the said mold release layer can be made smoother. In addition, when PET or paper is used as the release layer, there is a risk that problems such as curling will occur due to changes in the atmospheric temperature, workability will be impaired, and the appearance will be deteriorated. By using this, such a problem can be sufficiently prevented.

Among the olefin resin films, a polypropylene resin film is more preferable. Thereby, it is possible to further prevent the curling from occurring in the state of the product.

As the release agent used when the release treatment is performed, a silicone-based release agent is preferably used. What is necessary is just to set the thickness of the said mold release layer according to a combination with an adhesive layer or the objective, a use, etc.

The exterior film of the present invention is provided with functional layers such as a colored layer, a printing layer, an adhesive layer, and a printing support layer in addition to the base material and the topcoat layer for the purpose of improving the characteristics and the like. It may be provided. The positions of these layers can also be arbitrarily selected.

Examples of the adherend to which the exterior film of the present invention is applied include advertisements, signboards, exterior parts of various vehicles, metal products such as steel plates, resin products, and paper products.

Examples of the exterior film of the present invention are shown in FIGS.
FIG. 1 shows an example of a schematic view of an exterior film of the present invention having a two-layer structure. The exterior film shown in FIG. 1 is obtained by laminating a top coat layer 1 and a base material layer 2 in direct contact with each other without any other layers.
FIG. 2 shows an example of a schematic view of a state in which the exterior film of the present invention is attached to an adherend. The exterior film shown in FIG. 2 is obtained by attaching the top coat layer 1 and the base material layer 2 to the adherend 4 via the pressure-sensitive adhesive layer 3.

The manufacturing method of the exterior film of the present invention is not particularly limited, and can be manufactured by a conventionally known method, for example, extrusion molding, calendar molding, or the like. Specifically, for example, the composition for forming the base material layer is dissolved and kneaded at a temperature of 150 to 180 ° C. using a Banbury mixer, the obtained resin composition is supplied to a calendar, and a roll temperature of 160 It rolls at -200 degreeC and a base material layer is obtained. Next, after treating one side of the base material layer, a method for applying and curing the composition for forming the top coat layer on the treated side so as to obtain a predetermined thickness can be mentioned.
As a method for treating the base material layer, a conventionally known method may be used. For example, a corona treatment may be mentioned in terms of low equipment investment.

The corona treatment can be performed, for example, by passing a layer (olefin film layer) to be treated through a corona atmosphere generated in an inert gas using a known corona discharge treatment device. Corona discharge density at the time of the corona treatment, usually, 10 W · min / ^{m 2} or more, preferably a 30～300W · min / ^{m 2.} Examples of the inert gas include argon, helium, krypton, neon, xenon, nitrogen, and a mixture of two or more of these. Of these, nitrogen is preferred industrially. The inert gas may contain oxygen when the oxygen concentration in the gas is 1% by volume or less, preferably 0.1% by volume or less, more preferably 0.01% by volume or less.
Examples of the curing method include a method in which the temperature is set to 20 to 100 ° C.

Furthermore, the manufacturing method of the said exterior film is not specifically limited if it is a method which can laminate | stack an adhesive layer and a mold release layer as needed to a topcoat layer and a base material layer, for example, A method in which a pressure-sensitive adhesive layer is formed by applying a pressure-sensitive adhesive to the release layer, and then the pressure-sensitive adhesive layer is adhered (laminated) to a base material layer of a film composed of a topcoat layer and a base material layer is suitable. .

The exterior film of the present invention is an exterior film having a base layer formed using a polyolefin-based resin and a top coat layer formed using a polycarbonate-based urethane resin, the top coat layer being Since it is formed by mixing two specific types of isocyanate at a specific ratio, it is excellent in weather resistance, scratch resistance and chemical resistance, and is excellent in workability such as curved surface followability. Therefore, the exterior film of the present invention can be suitably applied as an exterior exterior film for signs, vehicles, and the like.

Since the exterior film of the present invention has the above-described configuration, it is excellent in weather resistance, scratch resistance, chemical resistance, and curved surface followability. Therefore, the exterior film of the present invention is suitably applied as an outdoor exterior film.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the examples, “parts” and “%” mean “parts by mass” and “% by mass” unless otherwise specified.

Example 1
(Creation of base material layer)
40 parts by mass of polypropylene resin (trade name: WT2002A, manufactured by Nippon Polypropylene) and 40 parts by mass of olefin-based thermoplastic elastomer (trade name: R-110E, manufactured by Idemitsu), low-density polyethylene resin (trade name: KF-280, 20 parts by mass of Nippon Polypropylene Co., Ltd. and 0.2 parts by mass of antioxidant (trade name: Irganox 1076, manufactured by Ciba Specialty Chemicals) and 0.2 part by mass of calcium stearate lubricant are mixed using a Banbury mixer. The resulting resin composition is melt-kneaded at a temperature of 150 to 180 ° C., supplied to a four-inverted L-roll type 24-inch calendar, rolled at a roll temperature of 160 to 190 ° C. to a thickness of 0.10 mm, A material layer was created.

(Formation of top coat layer)
After the substrate layer obtained above is subjected to corona discharge treatment, 100 parts by mass of a polycarbonate urethane resin (trade name: U5635G-3, manufactured by Seiko Kasei Co., Ltd.), 4.5 parts by mass of hexamethylene diisocyanate (HDI), isophorone diisocyanate. (IPDI) 0.5 parts by mass, a zinc catalyst (trade name: Nikka Octix zinc, zinc 2-ethylhexanoate, manufactured by Nippon Chemical Industry Co., Ltd.), a resin composition having a thickness after drying of 5 μm The film was coated and cured in a constant temperature room at 40 ° C. to obtain a film having a top coat layer formed thereon.

(Creation of exterior film)
Adhesive (acrylic: SK Dyne 1340, manufactured by Soken Chemical Co., Ltd.) is applied to release paper treated with a silicone release agent on high-quality paper of 110 g / m ² so that the thickness after drying is 30 μm. Then, the pressure-sensitive adhesive layer formed and dried was bonded to the film obtained above to obtain an exterior film having a release layer.

Examples 2 to 4 and Comparative Examples 1 to 3
In Example 1, a film was prepared in the same manner as in Example 1 except that the composition of the material for forming the top coat layer, the catalyst type, and the coating thickness were changed according to Table 1.
In addition, the used commercial item is as follows.
Tin (Sn) catalyst: N-100 manufactured by Nitto Kasei Co., Ltd.
Zirconium (Zr) catalyst: XC-4205 manufactured by KING INDUSTRIES

Comparative Example 4
Methyl methacrylate / alkyl acrylate copolymer (trade name: Parapet HR-A, manufactured by Kuraray Co., Ltd.) 50 parts by mass, methyl methacrylate / alkyl acrylate / styrene copolymer (trade name: Metabrene W341, manufactured by Mitsubishi Rayon Co., Ltd.) ) 50 parts by mass, antioxidant (trade name: Irganox 1076, manufactured by Ciba Specialty Chemicals) 1 part by mass, 0.2 parts by mass of calcium stearate as stabilizer, 0.2 parts by mass of zinc stearate, LS- as a lubricant 5 parts (manufactured by Asahi Denka Kogyo Co., Ltd.) are melt kneaded at a temperature of 150 to 180 ° C. using a Banbury mixer, and the resulting resin composition is supplied to a four-inverted L-roll type 24-inch calendar, Rolled to a thickness of 0.10 mm at a roll temperature of 170-200 ° C.

The obtained exterior film was evaluated by the following method. The results are shown in Table 1.
(Evaluation methods and criteria)
Scratch resistance A release layer was peeled off and an exterior film was affixed to an aluminum plate having a thickness of 1 mm, and then allowed to stand at room temperature for 5 days. The scratches on the film surface were visually confirmed with a Taber abrasion tester.
Abrasion wheel CS17 × load 1 kg × 3000 rotation was evaluated as “O” if no scratches were noticeable, and “X” if conspicuous.

Alcohol resistance 1 cc of isopropyl alcohol (99%) was dropped on the film (topcoat layer) and allowed to stand at 23C for 24 hours.
Thereafter, the surface was washed and the trace of dropping was visually confirmed.
If the trace was not conspicuous, it was rated as ○, if a slight trace was observed, Δ, and if the trace was conspicuous, x.

1 cc of acid- resistant 10% hydrochloric acid was dropped on the film (topcoat layer) and allowed to stand at 23 ° C. for 24 hours.
Thereafter, the surface was washed and the trace of dropping was visually confirmed.
If the trace was not conspicuous, it was rated as ○, if a slight trace was observed, Δ, and if the trace was conspicuous, x.

Weather resistance The appearance after accelerating for 2000 hours was visually confirmed with sunshine WOM (based on JIS-A-1415).
If the discoloration was not noticeable, it was rated as “◯”, if the discoloration was confirmed, “Δ”, and if there was a significant discoloration, “x”.

Heavy metal content: ◯ when no heavy metal was contained, and x when the heavy metal was contained.
After following the release layer and pasting each exterior film on an aluminum plate with a curved surface followability of 1 mm thickness, leave it at room temperature for 5 days, and use a round shape (round hat) with the outer diameter of 32 mm and the depth of 3 mm. The shape was drawn.
When there was no abnormality in appearance such as film floating, cracking, tearing, whitening, and partial elongation (necking), it was rated as ◯.

From Table 1, the films of the examples were good in all of scratch resistance, scratch resistance, chemical resistance and curved surface followability, but none of the films of the comparative examples were good. Therefore, in the examples, although it is non-PVC, it has flexibility like PVC, is excellent in scratch resistance, weather resistance, and chemical resistance, and is not whitened during bending or stretching in post-processing, and has a cubic curved surface. It was possible to provide an inexpensive outdoor exterior film that is easy to follow and can be used for deep drawing.

The exterior film of the present invention is suitably applied as a film for decorating signs and vehicles.

It is an example of the schematic of the film for exteriors of this invention. It is an example of the schematic of the state which affixed the film for exterior of this invention on the to-be-adhered body.

Explanation of symbols

1 Topcoat layer 2 Base material layer 3 Adhesive layer 4

Claims (5)

A base material layer formed using a polyolefin-based resin, and an exterior film having a topcoat layer,
The topcoat layer is formed using a polycarbonate urethane resin, hexamethylene diisocyanate and isophorone diisocyanate,
The exterior film, wherein a mixing ratio of the hexamethylene diisocyanate and the isophorone diisocyanate is 9: 1 to 6: 4 by mass ratio. The exterior film according to claim 1, wherein the top coat layer is formed using a zinc-based compound as a catalyst. The exterior film according to claim 1 or 2, wherein the top coat layer has a thickness of 2 to 50 µm. The exterior film of Claim 1, 2, or 3 which further has an adhesive layer. The exterior film according to claim 4, further comprising a release layer.

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